EP0714147B1 - High-temperature fuel cell with chromium-containing connecting elements between the electrochemical active plates - Google Patents

High-temperature fuel cell with chromium-containing connecting elements between the electrochemical active plates Download PDF

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Publication number
EP0714147B1
EP0714147B1 EP94810667A EP94810667A EP0714147B1 EP 0714147 B1 EP0714147 B1 EP 0714147B1 EP 94810667 A EP94810667 A EP 94810667A EP 94810667 A EP94810667 A EP 94810667A EP 0714147 B1 EP0714147 B1 EP 0714147B1
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EP
European Patent Office
Prior art keywords
connection element
chromium oxide
air
fuel cell
cover layer
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94810667A
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German (de)
French (fr)
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EP0714147A1 (en
Inventor
Dr. Emad Batawi
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Hexis AG
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Hexis AG
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Priority to DE59409325T priority Critical patent/DE59409325D1/en
Priority to EP94810667A priority patent/EP0714147B1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2432—Grouping of unit cells of planar configuration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
    • H01M8/0219—Chromium complex oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to the use of a Cover layer as a cover on a chrome-containing Connection element in a high temperature fuel cell.
  • Chromium-containing interconnectors (connecting elements) known, which are coated. Purpose of the coating is to protect metallic chrome from oxidation. From EP-A 0 410 166 and EP-A 0 423 448 Fasteners known, the surfaces with Precious metals are coated and one of which additional layer between a base body and the Precious metal coating provided as a diffusion barrier is.
  • the invention is based on a fuel cell EP-A 0 551 054 is known: It has proven to be proven to be advantageous on both sides of the electrochemical active plate - the so-called PEN - one each Arrange metallic interconnector with knob-like elements an electrical connection the electrode of the PEN. These interconnectors have a triple function, namely as a current collector, Temperature compensation means and heat exchanger element for the fed air. Because of the high operating temperature and because of the formation of metal oxides on the Surface of the interconnectors need alloys be used, which are at least from around 25% chromium exist and form a chromium oxide protective layer. The Use of aluminides, even at elevated Temperatures would be out of the question. Because aluminum oxide is in contrast to chromium oxide electrically non-conductive.
  • This task is achieved by using a cover layer Claim 1 or 2 solved. Because of this use the air carries little in a special cover layer gaseous chromium oxide with it. Any deposits Chromium oxide on the electrodes are removed from the PEN surfaces desorbed and from the low chromium oxide air transported out of the system. Thanks to the low Chromium oxide concentration in the air only occurs not harmful chrome oxide deposits.
  • the independent claim 3 relates to an analog Using a top layer in a battery Fuel cells, which also for an outside of the cells arranged heat exchanger wall measure according to the invention, namely the attachment of a of the chromium oxide barriers mentioned is provided.
  • a fuel cell 1 is shown in FIGS. 1 and 2 following components shown: an electrochemical active plate or PEN 2 coming from the air electrode or cathode 2c (see FIG. 3), the gas electrode or Builds anode 2a and the solid electrolyte 2b; on air-side interconnector 3; a gas side Interconnector 4; and an intermediate piece 5.
  • an electrochemical active plate or PEN 2 coming from the air electrode or cathode 2c (see FIG. 3), the gas electrode or Builds anode 2a and the solid electrolyte 2b; on air-side interconnector 3; a gas side Interconnector 4; and an intermediate piece 5.
  • air (arrow 35a) becomes sector-shaped Chambers 52 between interconnectors 3 and 4 fed.
  • Adjacent chambers 52 are radial Web 51 of the intermediate piece 5 separately. In these chambers 52 the air is heated to practically Operating temperatur.
  • Through an opening 33 in The air flows in the central region of the fuel cell 1 (Arrow 33a) in the space 32 between the PEN 2 and the Interconnector 2, which over the knob-like elements 31st connected to the PEN 2.
  • the free surfaces 30a and 310 of one layer coated which acts as a barrier to chromium oxide.
  • the inner surfaces 304 and 403 (see Fig. 2) of the chambers 52 are coated in the same way.
  • the gas-side interconnector 4 is of the same design like the air side 2; in Fig. 1 is the dot-dash line Level 4 'shown in the knob-like elements 41st (see Fig.2) with the gas electrode of the PEN 2 one adjacent cell are connected. The corresponding The plane for the air side has the reference symbol 3 '.
  • the fuel cell 1 forms the repetitive one Element of a stack that is related to an axis 11 is formed centrally symmetrical. Via a central Channel 45 becomes the gaseous fuel, or gas 5 for short (Arrow 45a), into spaces 42 between PEN 2 and Interconnector 4 supplied.
  • FIG. 3 shows part of the three-layer PEN 2, with the anode 2a, the Solid electrolytes 2b and the cathode 2c.
  • the Interconnector 3 (through a layer 7 with the PEN 2 connected.
  • Layer 7 is porous; it is from one Slurry of a suitable powdery substance manufactured. Such substances are from EP-A 0 556 532 known.
  • connection layer 7 is shown in FIG adjacent layers as a cross section for a known Fuel cell shown.
  • CrO3 is gaseous chromium oxide CrO3 from layer 6 in the Airspace 32 released (arrows 61).
  • the concentration of the CrO3 in room 32 is stored Chromium oxide partly on the cathode 2c in the form of Cr2O3 down (arrows 62).
  • Such deposits 63 affect the current supplying cathode reactions. With the arrow 3a the electron transport is indicated.
  • chromium oxide barrier 8 can have a certain permeability to chromium oxide 5 (Arrow 61 '); because the released chromium oxide is from the Air is taken up in room 32 and transported away.
  • a fuel cell battery is known from EP-A 0 580 918 known with a heat-insulating cover; such a
  • the device is shown in detail in FIG. in the Annular gap between the stack. 10 with cells 1 and a combustion chamber 13 is a cylindrical wall 12 arranged where the gas is not completely consumed is burned.
  • the air gets under heat through a channel system 18, 15 of the heat-insulating shell 17, 14 in the annular space 16 where it is on the wall 12 is further heated before it goes over the pipes 35 in the individual fuel cells occurs. So the air does not pick up chromium oxides from the wall 12, this is also Wall 12 coated with a chromium oxide barrier.
  • Suitable ceramic materials are perovskites, in particular magnetite (La, Sr) MnO 3 , chromite (La, Sr) CrO 3 or cobaltite (La, Sr) CoO 3 .
  • a quantity of 100g perovskite powder is mixed with around 50g organic substances, which evaporate again when the applied layer dries and sinters.
  • organic substances mainly consist of around 35 g of a solvent (e.g. DEGBEA: diethylene glycol monobutyl ether acetate).
  • Additives are, for example, deflocculants (eg "Beycostat”) and / or substances with which the rheological properties of the slurry can be influenced (eg furan-2-carboxylic acid). Details of the problem of ceramic slurries can be found in a publication by JSReed, Introduction to the Principles of Ceramic Processing, J.Wiley, NY, 1987.
  • Ceramic powders instead of ceramic powders, metallic ones can be used Use powder with carbonates added to it are. The metals are oxidized during the heat treatment and thereby converted into a ceramic phase.
  • the enamel layers are made from a glass powder (particle size around 0.5 ⁇ m), which is slurried, for example, in terpineol, whereby - as with the ceramic material - a deflocculant is advantageously added to this solvent.
  • Compositions are suitable for the glass, as given by the following list: SiO 2 (40-60), Al 2 O 3 and / or Y 2 O 3 (0-10), CaO (0-10), Na 2 O (0-15), MnO (10-25), CoO (0-10), the expressions in the parentheses denoting percentages by weight.
  • Galvanic deposition coating by vapor deposition / sputtering or thermal spraying.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Description

Die Erfindung bezieht sich auf eine Verwendung einer Deckschicht als Abdeckung auf einem chromhaltigen Verbindungselement in einer Hochtemperatur-Brennstoffzelle.The invention relates to the use of a Cover layer as a cover on a chrome-containing Connection element in a high temperature fuel cell.

Aus der EP-A 0 338 823 und der JP-A 4138670 sind chromhaltige Interkonnektoren (Verbindungselemente) bekannt, die beschichtet sind. Zweck der Beschichtung ist, metallisches Chrom vor einer Oxidation zu schützen. Aus den EP-A 0 410 166 und EP-A 0 423 448 sind Verbindungselemente bekannt, deren Oberflächen mit Edelmetallen beschichtet sind und bei denen eine zusätzliche Schicht zwischen einem Grundkörper und der Edelmetallbeschichtung als Diffusionssperre vorgesehen ist.From EP-A 0 338 823 and JP-A 4138670 Chromium-containing interconnectors (connecting elements) known, which are coated. Purpose of the coating is to protect metallic chrome from oxidation. From EP-A 0 410 166 and EP-A 0 423 448 Fasteners known, the surfaces with Precious metals are coated and one of which additional layer between a base body and the Precious metal coating provided as a diffusion barrier is.

Die Erfindung geht von einer Brennstoffzelle aus, die aus der EP-A 0 551 054 bekannt ist: Es hat sich als vorteilhaft erwiesen, beiderseits der elektrochemisch aktiven Platte - dem sogenannten PEN - jeweils einen metallischen Interkonnektor anzuordnen, der mit noppenartigen Elementen eine elektrische Verbindung zu der Elektrode des PEN herstellt. Diese Interkonnektoren haben eine dreifache Funktion, nämlich als Stromsammler, Temperaturausgleichsmittel und Wärmetauscherelement für die eingespeiste Luft. Wegen der hohen Betriebstemperatur und wegen der Ausbildung von Metalloxiden an der Oberfläche der Interkonnektoren müssen Legierungen verwendet werden, die mindestens aus rund 25 % Chrom bestehen und die eine Chromoxid-Schutzschicht bilden. Die Verwendung von Aluminiden, die auch bei erhöhten Temperaturen einsetzbar wären, kommen nicht in Frage. Denn Aluminiumoxid ist im Gegensatz zu Chromoxid elektrisch nicht leitend. The invention is based on a fuel cell EP-A 0 551 054 is known: It has proven to be proven to be advantageous on both sides of the electrochemical active plate - the so-called PEN - one each Arrange metallic interconnector with knob-like elements an electrical connection the electrode of the PEN. These interconnectors have a triple function, namely as a current collector, Temperature compensation means and heat exchanger element for the fed air. Because of the high operating temperature and because of the formation of metal oxides on the Surface of the interconnectors need alloys be used, which are at least from around 25% chromium exist and form a chromium oxide protective layer. The Use of aluminides, even at elevated Temperatures would be out of the question. Because aluminum oxide is in contrast to chromium oxide electrically non-conductive.

Wie sich herausgestellt hat, erleiden die elektrochemisch aktiven Platten in Anwesenheit von chromhaltigen Legierungen allmählich eine Leistungseinbusse. Der Abbau des Wirkungsgrades ist darauf zurückzuführen, dass bei den Betriebstemperaturen Chromoxid in die Gasphase übergeht, aus der sich das Chromoxid auf die Elektroden des PEN niederschlägt.As it turned out, they suffer electrochemically active plates in the presence of chromium-containing Alloys gradually lose performance. The mining the efficiency is due to the fact that at the operating temperatures chromium oxide in the gas phase passes from which the chromium oxide to the electrodes of the PEN.

Es ist Aufgabe der Erfindung, Mittel zu schaffen, durch die der Transport von Chromoxid von den Interkonnektoren zu den PEN-Elektroden unterbunden wird. Diese Aufgabe wird mittels einer Verwendung einer Deckschicht gemäss Anspruch 1 oder 2 gelöst. Aufgrund dieser Verwendung einer besonderen Deckschicht führt die Luft nur wenig gasförmiges Chromoxid mit sich. Allfällige Ablagerungen von Chromoxid auf den Elektroden werden von den PEN-Oberflächen desorbiert und von der chromoxidarmen Luft aus dem System wegtransportiert. Dank der niedrigen Chromoxidkonzentration in der Luft kommt es erst gar nicht zu schädlichen Chromoxidablagerungen.It is an object of the invention to provide means by which is the transportation of chromium oxide from the interconnectors to the PEN electrodes is prevented. This task is achieved by using a cover layer Claim 1 or 2 solved. Because of this use the air carries little in a special cover layer gaseous chromium oxide with it. Any deposits Chromium oxide on the electrodes are removed from the PEN surfaces desorbed and from the low chromium oxide air transported out of the system. Thanks to the low Chromium oxide concentration in the air only occurs not harmful chrome oxide deposits.

Der unabhängige Anspruch 3 bezieht sich auf eine analoge Verwendung einer Deckschicht in einer Batterie mit Brennstoffzellen, bei welcher auch für eine ausserhalb der Zellen angeordnete Wärmetauscherwand die erfindungsgemässe Massnahme, nämlich das Anbringen einer der genannten Chromoxid-Barrieren, vorgesehen ist.The independent claim 3 relates to an analog Using a top layer in a battery Fuel cells, which also for an outside of the cells arranged heat exchanger wall measure according to the invention, namely the attachment of a of the chromium oxide barriers mentioned is provided.

Nachfolgend wird die Erfindung anhand der Zeichnungen erläutert. Es zeigen:

Fig. 1
eine aufgebrochene Brennstoffzelle,
Fig. 2
einen Querschnitt durch die Brennstoffzelle,
Fig. 3
ausschnittsweise einen Interkonnektor der Brennstoffzelle mit PEN,
Fig. 4
einen Querschnitt durch eine Kontaktstelle zwischen PEN und Interkonnektor für eine bekannte Brennstoffzelle,
Fig. 5
einen Querschnitt wie in Fig.4 für eine erfindungsgemässe Brennstoffzelle und
Fig.6
einen Ausschnitt eines Stapels von Brennstoffzellen.
The invention is explained below with reference to the drawings. Show it:
Fig. 1
a broken fuel cell,
Fig. 2
a cross section through the fuel cell,
Fig. 3
sections of an interconnector of the fuel cell with PEN,
Fig. 4
3 shows a cross section through a contact point between the PEN and the interconnector for a known fuel cell,
Fig. 5
a cross section as in Figure 4 for a fuel cell according to the invention and
Fig. 6
a section of a stack of fuel cells.

In den Figuren 1 und 2 ist eine Brennstoffzelle 1 mit folgenden Komponenten gezeigt: eine elektrochemisch aktive Platte oder PEN 2, die sich aus der Luftelektrode oder Kathode 2c (siehe Fig. 3), der Gaselektrode oder Anode 2a und dem Feststoffelektrolyten 2b aufbaut; ein luftseitiger Interkonnektor 3; ein gasseitiger Interkonnektor 4; und ein Zwischenstück 5.A fuel cell 1 is shown in FIGS. 1 and 2 following components shown: an electrochemical active plate or PEN 2 coming from the air electrode or cathode 2c (see FIG. 3), the gas electrode or Builds anode 2a and the solid electrolyte 2b; on air-side interconnector 3; a gas side Interconnector 4; and an intermediate piece 5.

Über Rohre 35 wird Luft (Pfeil 35a) in sektorförmige Kammern 52 zwischen den Interkonnektoren 3 und 4 eingespeist. Benachbarte Kammern 52 sind durch radiale Stege 51 des Zwischenstücks 5 getrennt. In diesen Kammern 52 erfolgt eine Erwärmung der Luft auf praktisch Betriebstemperatur. Durch eine Öffnung 33 im Mittenbereich der Brennstoffzelle 1 strömt die Luft (Pfeil 33a) in den Raum 32 zwischen dem PEN 2 und dem Interkonnektor 2, der über die noppenartigen Elemente 31 mit dem PEN 2 in Verbindung steht. Erfindungsgemäss sind die freien Oberflächen 30a und 310 von einer Schicht überzogen, die als Barriere für Chromoxid wirkt. Auch die inneren Oberflächen 304 und 403 (siehe Fig. 2) der Kammern 52 sind in gleicher Art beschichtet. Via pipes 35, air (arrow 35a) becomes sector-shaped Chambers 52 between interconnectors 3 and 4 fed. Adjacent chambers 52 are radial Web 51 of the intermediate piece 5 separately. In these chambers 52 the air is heated to practically Operating temperatur. Through an opening 33 in The air flows in the central region of the fuel cell 1 (Arrow 33a) in the space 32 between the PEN 2 and the Interconnector 2, which over the knob-like elements 31st connected to the PEN 2. According to the invention the free surfaces 30a and 310 of one layer coated, which acts as a barrier to chromium oxide. Also the inner surfaces 304 and 403 (see Fig. 2) of the chambers 52 are coated in the same way.

Der gasseitige Interkonnektor 4 ist gleich ausgebildet wie der luftseitige 2; in Fig.1 ist strichpunktiert die Ebene 4' dargestellt, in der noppenartige Elemente 41 (siehe Fig.2) mit der Gaselektrode des PEN 2 einer benachbarten Zelle verbunden sind. Die entsprechende Ebene für die Luftseite hat das Bezugszeichen 3'.The gas-side interconnector 4 is of the same design like the air side 2; in Fig. 1 is the dot-dash line Level 4 'shown in the knob-like elements 41st (see Fig.2) with the gas electrode of the PEN 2 one adjacent cell are connected. The corresponding The plane for the air side has the reference symbol 3 '.

Die Brennstoffzelle 1 bildet das sich wiederholende Element eines Stapels, der bezüglich einer Achse 11 zentralsymmetrisch ausgebildet ist. Über einen zentralen Kanal 45 wird der gasförmige Brennstoff, kurz das Gas 5 (Pfeil 45a), in die Räume 42 zwischen PEN 2 und Interkonnektor 4 zugeführt.The fuel cell 1 forms the repetitive one Element of a stack that is related to an axis 11 is formed centrally symmetrical. Via a central Channel 45 becomes the gaseous fuel, or gas 5 for short (Arrow 45a), into spaces 42 between PEN 2 and Interconnector 4 supplied.

Die Detaildarstellung in Fig.3 zeigt einen Teil des dreischichtigen PEN 2, mit der Anode 2a, dem Feststoffelektrolyten 2b und der Kathode 2c. Der Interkonnektor 3 ist (durch eine Schicht 7 mit dem PEN 2 verbunden. Die Schicht 7 ist porös; sie ist aus einer Aufschlämmung eines geeigneten pulverförmigen Stoffs hergestellt. Solche Stoffe sind aus der EP-A 0 556 532 bekannt.The detailed representation in Figure 3 shows part of the three-layer PEN 2, with the anode 2a, the Solid electrolytes 2b and the cathode 2c. The Interconnector 3 (through a layer 7 with the PEN 2 connected. Layer 7 is porous; it is from one Slurry of a suitable powdery substance manufactured. Such substances are from EP-A 0 556 532 known.

Die Verbindungsschicht 7 ist in Fig.4 zusammen mit benachbarten Schichten als Querschnitt für eine bekannte Brennstoffzelle dargestellt. Eine dünne Schicht 6 aus Chromoxid Cr2O3, überzieht den Interkonnektor 3. Bei den Betriebstemperaturen der Hochtemperatur-Brennstoffzelle wird gasförmiges Chromoxid CrO3 von der Schicht 6 in den Luftraum 32 freigesetzt (Pfeile 61). Bei hohen Konzentrationen des CrO3 im Raum 32 lagert sich das Chromoxid teilweise auf der Kathode 2c in Form von Cr2O3 ab (Pfeile 62). Solche Ablagerungen 63 beeinträchtigen die stromliefernden Kathodenreaktionen. Mit dem Pfeil 3a ist der Elektronentransport angedeutet. The connection layer 7 is shown in FIG adjacent layers as a cross section for a known Fuel cell shown. A thin layer 6 out Chromium oxide Cr2O3, covers the interconnector 3. At the Operating temperatures of the high temperature fuel cell is gaseous chromium oxide CrO3 from layer 6 in the Airspace 32 released (arrows 61). At high The concentration of the CrO3 in room 32 is stored Chromium oxide partly on the cathode 2c in the form of Cr2O3 down (arrows 62). Such deposits 63 affect the current supplying cathode reactions. With the arrow 3a the electron transport is indicated.

Wird - wie in Fig.5 gezeigt - die Oberfläche des Interkonnektors 3 gemäss der Erfindung mit einer Chromoxid-Barriere 8 beschichtet, so ergeben sich nur noch Chromoxid-Ablagerungen 64 in den Porenräumen zwischen der Verbindungsschicht 7 und der Kathode 2c. Der Wirkungsgrad der elektrochemisch aktiven Platte 2 ist nicht mehr beeinträchtig. Die Chromoxid-Barriere 8 kann eine gewisse Durchlässigkeit für Chromoxid aufweisen 5 (Pfeil 61'); denn das freigesetzte Chromoxid wird von der Luft im Raum 32 aufgenommen und wegtransportiert.If - as shown in Fig. 5 - the surface of the Interconnector 3 according to the invention with a Chromium oxide barrier 8 coated, only result still chromium oxide deposits 64 in the pore spaces between the connection layer 7 and the cathode 2c. The Efficiency of the electrochemically active plate 2 is no longer affected. The chromium oxide barrier 8 can have a certain permeability to chromium oxide 5 (Arrow 61 '); because the released chromium oxide is from the Air is taken up in room 32 and transported away.

Aus der EP-A 0 580 918 ist eine Brennstoffzellen-Batterie mit einer wärmedämmenden Hülle bekannt; eine derartige Vorrichtung ist in Fig.6 ausschnittsweise dargestellt. Im Ringspalt zwischen dem Stapel. 10 mit den Zellen 1 und einer zylindrischen Wand 12 ist ein Verbrennungsraum 13 angeordnet, wo das nicht vollständig verbrauchte Gas nachverbrannt wird. Die Luft gelangt unter Wärmeaufnahme durch ein Kanalsystem 18, 15 der wärmedämmenden Hülle 17, 14 in den ringspaltförmigen Raum 16, wo sie an der Wand 12 weiter aufgeheizt wird, bevor sie über die Rohre 35 in die einzelnen Brennstoffzellen eintritt. Damit die Luft nicht Chromoxide von der Wand 12 aufnimmt, ist auch diese Wand 12 mit einer Chromoxid-Barriere beschichtet.A fuel cell battery is known from EP-A 0 580 918 known with a heat-insulating cover; such a The device is shown in detail in FIG. in the Annular gap between the stack. 10 with cells 1 and a combustion chamber 13 is a cylindrical wall 12 arranged where the gas is not completely consumed is burned. The air gets under heat through a channel system 18, 15 of the heat-insulating shell 17, 14 in the annular space 16 where it is on the wall 12 is further heated before it goes over the pipes 35 in the individual fuel cells occurs. So the air does not pick up chromium oxides from the wall 12, this is also Wall 12 coated with a chromium oxide barrier.

Als Material für die Chromoxid-Barrieren kommen keramische Stoffe oder Silikatgläser in Frage. Diese Stoffe werden nach bekannten Methoden als aufgeschlämmte Pulver ("Slurry") auf die abzudeckenden Oberflächen aufgetragen. Nach dem Trocknen werden die aufgetragenen Schichten mittels Wärmebehandlung durch Versintern oder Schmelzen zu einer dichten Deckschicht umgeformt.Coming as material for the chrome oxide barriers ceramic fabrics or silicate glasses in Question. These substances are known as slurried powder ("slurry") on the to be covered Surfaces applied. After drying, the applied layers by means of heat treatment Sinter or melt into a dense top layer reshaped.

Geeignete keramische Stoffe sind Perowskite, insbesondere Magnetit (La,Sr)MnO3, Chromit (La,Sr)CrO3 oder Kobaltit (La,Sr)CoO3. Einer Menge von 100g Perowskit-Pulver werden rund 50g organische Stoffe zugemischt, die sich beim Trocknen und Sintern der aufgetragenen Schicht wieder verflüchtigen. Die organischen Stoffe bestehen neben Bindemitteln (z.B. Ethyl-Zellulose) und Zusatzstoffen hauptsächlich - zu rund 35 g - aus einem Lösungsmittel (z.B. DEGBEA: Diethylen-Glycol-Monobutyl-Ether-Acetat). Zusatzstoffe sind beispielsweise Entflockungsmittel (z.B. "Beycostat") und/oder Stoffe, mit denen sich die rheologischen Eigenschaften der Aufschlämmung beeinflussen lassen (z.B. Furan-2-Carboxyl-Säure). Details zum Problemkreis der keramischen Aufschlämmungen findet man in einer Druckschrift von J.S.Reed, Introduction to the Principles of Ceramic Processing, J.Wiley, N.Y., 1987.Suitable ceramic materials are perovskites, in particular magnetite (La, Sr) MnO 3 , chromite (La, Sr) CrO 3 or cobaltite (La, Sr) CoO 3 . A quantity of 100g perovskite powder is mixed with around 50g organic substances, which evaporate again when the applied layer dries and sinters. In addition to binders (e.g. ethyl cellulose) and additives, the organic substances mainly consist of around 35 g of a solvent (e.g. DEGBEA: diethylene glycol monobutyl ether acetate). Additives are, for example, deflocculants (eg "Beycostat") and / or substances with which the rheological properties of the slurry can be influenced (eg furan-2-carboxylic acid). Details of the problem of ceramic slurries can be found in a publication by JSReed, Introduction to the Principles of Ceramic Processing, J.Wiley, NY, 1987.

Anstelle von keramischen Pulvern lassen sich metallische Pulver verwenden, denen mit Vorteil Carbonate beigemengt sind. Bei der Wärmebehandlung werden die Metalle oxidiert und dadurch in eine keramische Phase umgewandelt.Instead of ceramic powders, metallic ones can be used Use powder with carbonates added to it are. The metals are oxidized during the heat treatment and thereby converted into a ceramic phase.

Die Emailschichten werden aus einem Glaspulver (Partikelgrösse rund 0.5µm) hergestellt, das beispielsweise in Terpineol aufgeschlämmt ist, wobei mit Vorteil - wie beim keramischen Material - diesem Lösungsmittel ein Entflockungsmittel beigemischt ist. Für das Glas kommen Zusammensetzungen in Frage, wie sie durch folgende Aufstellung gegeben sind: SiO2 (40-60), Al2O3 und/oder Y2O3 (0-10), CaO (0-10), Na2O (0-15), MnO (10-25), CoO (0-10), wobei die Ausdrücke in den Klammern Gewichtsprozent-Bereiche bedeuten.The enamel layers are made from a glass powder (particle size around 0.5µm), which is slurried, for example, in terpineol, whereby - as with the ceramic material - a deflocculant is advantageously added to this solvent. Compositions are suitable for the glass, as given by the following list: SiO 2 (40-60), Al 2 O 3 and / or Y 2 O 3 (0-10), CaO (0-10), Na 2 O (0-15), MnO (10-25), CoO (0-10), the expressions in the parentheses denoting percentages by weight.

Es sind auch andere Beschichtungsverfahren möglich: Galvanische Abscheidung, Beschichtung durch Aufdampfen/Sputtern oder thermische Spritzverfahren.Other coating processes are also possible: Galvanic deposition, coating by vapor deposition / sputtering or thermal spraying.

Claims (3)

  1. Use of a cover layer (8) as a cover on a chromium containing connection element (3) in a high-temperature fuel cell (1), wherein the connection element is provided for an electrically conductive connection from the cathode (2c) of an electrochemically active plate (2) to the anode (2a) of a corresponding plate (2) in a neighbouring cell (1), the connection element is formed as a heat exchanger for the heating of air (35a, 33a) for cathode reactions, and the surface of the connection element has chromium oxide as a protective layer against an oxidation, wherein the cover layer (8) covers over exposed surfaces of the connection element which come into contact with the air to be heated in order to act as a barrier for chromium oxide at the operating temperatures of the fuel cell, characterized in that the cover layer (8) consists at least partly of a perovskite, in particular of magnetite (La, Sr)MnO3, chromite (La, Sr)SrO3 or cobaltite (La, Sr)CoO3.
  2. Use of a cover layer (8) as a cover on a chromium containing connection element (3) in a high-temperature fuel cell (1), wherein the connection element is provided for an electrically conductive connection from the cathode (2c) of an electrochemically active plate (2) to the anode (2a) of a corresponding plate (2) in a neighbouring cell (1), the connection element is formed as a heat exchanger for the heating of air (35a, 33a) for cathode reactions, and the surface of the connection element has chromium oxide as a protective layer against an oxidation, wherein the cover layer (8) covers over exposed surfaces of the connection element which come into contact with the air to be heated in order to act as a barrier for chromium oxide at the operating temperatures of the fuel cell, characterized in that the cover layer (8) consists at least partly of an enamel which is composed of the following substances, with ranges for possible percentages by weight being set forth in brackets: SiO2 (40-60), Al2O3 and/or Y2O3 (0-10), CaO (0-10), Na2O (0-15), MnO (10-25), CoO (0-10).
  3. Use of a cover layer as chromium oxide barrier in a battery with a cylindrical stack of fuel cells (1) and an afterburning space (13), wherein a connection element is provided in each cell for an electrically conductive connection from the cathode (2c) of an electrochemically active plate (2) to the anode (2a) of a corresponding plate (2) in a neighbouring cell (1), the connection element is formed as a heat exchanger for the heating of air (35a, 33a) for cathode reactions and the surface of the connection element has chromium oxide as a protective layer against an oxidation, wherein furthermore the afterburning space is arranged at the side surface of the cell stack and a heat exchanger wall (12) of the afterburning space, which is provided for the heating up of air for the cathode reactions, is coated at least partly with a perovskite in accordance with claim 1 or an enamel in accordance with claim 2.
EP94810667A 1994-11-23 1994-11-23 High-temperature fuel cell with chromium-containing connecting elements between the electrochemical active plates Expired - Lifetime EP0714147B1 (en)

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